CN111604046B - Bismuth-based nano material and preparation method and application thereof - Google Patents

Bismuth-based nano material and preparation method and application thereof Download PDF

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CN111604046B
CN111604046B CN202010549277.5A CN202010549277A CN111604046B CN 111604046 B CN111604046 B CN 111604046B CN 202010549277 A CN202010549277 A CN 202010549277A CN 111604046 B CN111604046 B CN 111604046B
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CN111604046A (en
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李宇航
李春忠
王雅婷
程玲
刘锦泽
肖楚倩
陈容振
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East China University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/18—Arsenic, antimony or bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J35/33—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide

Abstract

The invention discloses a bismuth-based nano material and a preparation method and application thereof. The preparation method comprises the following steps: preparing nano-rod-shaped bismuth sulfide into a nano-sheet bismuth-based material by an electrochemical reduction method; the nano-rod-shaped bismuth sulfide is Bi (S) 2 CNEt 2 ) 3 Prepared by a hydrothermal method. The bismuth-based nano material solves the problem of low concentration of oxygen active ingredients in the subsurface solvent, and realizes good CO 2 Electrocatalytic reduction efficiency.

Description

Bismuth-based nano material and preparation method and application thereof
Technical Field
The invention relates to a bismuth-based nano material and a preparation method and application thereof.
Background
With the progress of times and the development of science and technology, energy has become an important factor affecting human society. At present, traditional energy sources such as coal, petroleum, natural gas and the like still play a very important role in the economic development of the world, but the reserves of the resources on the earth are very limited, and the energy crisis becomes a problem to be solved urgently by human beings at present. CO in the atmosphere 2 Is a main greenhouse gas causing global warming, people increasingly pay attention to the adverse effect of modern industrialization on human society, and rising CO 2 The amount of emissions poses a great threat to the global ecological environment. Electrochemical catalytic reduction for CO recovery 2 Has great economic and environmental benefits. However, due to the unavoidable hydrogen evolution reaction with CO in the aqueous solution 2 Competition of reduction reaction, slow kinetic process, high overpotential, and practical application of the method still face many challenges. Therefore, the development of highly selective electrocatalysts has become a key to the research in this field.
In CO 2 Among products of the electrocatalytic reduction reaction, formate is an important non-toxic product and has the advantages of easy collection and high hydrogen storage capacity. Metals such as bismuth, tin and indium have been shown to convert CO in aqueous electrolytes 2 An efficient catalyst for reduction to formate. They have a high overpotential for hydrogen evolution and are resistant to CO 2 ·- The intermediate is less avidity and tends to protonate at the carbon atom and eventually convert to formic acid. Bismuth has the property of being non-toxic and environmentally benign, however, direct control of the local coordination structure of bismuth is experimentally challenging due to its low melting point and susceptibility to oxidation upon exposure to air. Koh et al propose a rational design method for a layered Bi dendritic catalyst for CO 2 Electrocatalytic reduction of (ACS Catal.,2017,7, p. 5071-5077). In addition, a series of bismuth-based materials (e.g., bi) derived from bismuth-based composites 2 O 2 CO 3 ，Bi 2 O 3 BiOI) has been successfully applied to CO 2 Electrocatalytic reduction of (c). These materials may be converted, in whole or in part, to metallic bismuth in situ, with the subsurface of the material being intercalated with solvent oxygen to form a bismuth-oxygen bonded structure. The bismuth-oxygen bonding structure being CO 2 The main active ingredient of electrocatalytic reduction, but the low concentration of oxygen in the sub-surface solvent of the bismuth-based material limits the bismuth-based material in CO 2 Further improving the efficiency of the electrocatalytic reduction.
Disclosure of Invention
The invention aims to solve the problems that the bismuth-based material in the prior art has low concentration of oxygen in a subsurface solvent, and limits the existence of the bismuth-based material in CO 2 The problem of improving the electrocatalytic reduction efficiency, and provides a bismuth-based nano material with high-concentration subsurface solvent oxygen, a preparation method and application thereof.
In order to solve the above technical problems, the present invention provides the following technical solutions.
The preparation method of the bismuth-based nano material comprises the following steps: preparing nano-rod-shaped bismuth sulfide into a nano-sheet bismuth-based material by an electrochemical reduction method; the nano-rod-shaped bismuth sulfide is Bi (S) 2 CNEt 2 ) 3 Prepared by a hydrothermal method.
In the present invention, generally, the length of the nanorod-shaped bismuth sulfide may be in the range of 1 μm to 7 μm, and the width thereof may be in the range of 50nm to 400nm.
In the invention, the conditions of the hydrothermal method are the conditions for preparing the bismuth sulfide nano-rod conventionally in the field. Preferably, the hydrothermal process is carried out at a temperature in the range of 120 to 160 ℃ and for a time in the range of 6 to 24 hours; more preferably, the temperature of the hydrothermal process is 140 ℃ and the time is 10 hours.
Wherein, the Bi (S) 2 CNEt 2 ) 3 The amount of deionized water used in the hydrothermal method is conventional in the art, and can be 4 to 10g/100mL; preferably 6.5g/100mL.
In the present invention, the Bi (S) is 2 CNEt 2 ) 3 Can be prepared according to the conventional method in the field, for example, by mixing the solution of the bismuth source precursor and the solution of the sulfur source precursor.
Preferably, the bismuth source precursor is selected from bismuth nitrate and/or bismuth chloride, such as bismuth nitrate pentahydrate; the sulfur source precursor is selected from sodium diethyldithiocarbamate.
Preferably, the molar ratio of the bismuth source precursor to the sulfur source precursor is 1:1 to 1:5; more preferably, the molar ratio of the bismuth source precursor to the sulfur source precursor is 1:3.
preferably, the concentration of the bismuth source precursor is 0.1mol/L; the concentration of the sulfur source precursor is 0.1mol/L.
Preferably, the solvents in the solutions of the bismuth source precursor and the sulfur source precursor are conventional in the art, such as water or methanol, preferably methanol.
Preferably, the mixing is stirring at room temperature (e.g., 25 ℃).
In a preferred embodiment, the Bi (S) 2 CNEt 2 ) 3 The preparation method comprises the following steps: 33mL of 0.1mol/L bismuth source precursor solution was added dropwise to 100mL of 0.1mol/L sodium diethyldithiocarbamate solution.
In the present invention, the electrochemical reduction method is an electrochemical reduction method conventionally known in the art, and generally refers to a method of electrochemically reducing bismuth sulfide to bismuth/bismuth oxide.
Preferably, the electrochemical reduction method comprises the following: dispersing nano rod-shaped bismuth sulfide and 5wt% of perfluorosulfonic acid-polytetrafluoroethylene copolymer solution in ethanol, performing ultrasonic treatment to prepare a working electrode, and performing in-situ electrochemical reduction by using Ag/AgCl (3M KCl) as a reference electrode and a platinum electrode (such as a platinum mesh) as a counter electrode.
Wherein, the perfluorinated sulfonic acid-polytetrafluoroethylene copolymer solution is also called Nafion solution and is generally available on the market.
Wherein the dosage of the nano-rod-shaped bismuth sulfide and 5wt% of perfluorosulfonic acid-polytetrafluoroethylene copolymer solution is conventional in the field and can be 0.1-2 mg/mu L; preferably 0.25 mg/. Mu.L.
Wherein the dosage of the ethanol is conventional in the field, and the dosage of the nano rod-shaped bismuth sulfide relative to the ethanol is 1-50 mg/mL, preferably 10mg/mL.
Wherein the ultrasonic conditions are conventional in the field, for example, the ultrasonic frequency is 10-50 KHz, and the ultrasonic time is 20-60 minutes; preferably, the ultrasonic frequency is 40KHz and the ultrasonic time is 30 minutes.
Wherein the fabrication of the working electrode is a routine operation in the art, the ethanol dispersion is generally uniformly drop-coated on a hydrophobic carbon paper, such as 1 × 1cm 2 And (4) finishing.
Wherein the reduction potential of the electrochemical reduction is conventionally used in the art and may be-0.6 to-1.0V relative to the reversible hydrogen electrode, and preferably the reduction potential is-1.0V.
The time for the electrochemical reduction is, among others, conventional in the art and may range from 20 to 60 minutes, preferably 30 minutes.
The invention also provides a bismuth-based nano material prepared by the preparation method.
In the invention, the bismuth-based nano material is generally in a nano sheet shape, the length and the width of the bismuth-based nano material are 1-10 mu m, and the thickness of the bismuth-based nano material is 20-50 nm; through determination, the surface of the material has high-concentration subsurface solvent oxygen, and the content is 10% -15%.
The invention also provides the application of the bismuth-based nano material in electrocatalysis of CO 2 The application as a catalyst in reduction.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) The bismuth-based material has high-concentration subsurface solvent and good electrocatalysis CO 2 The reduction performance and stability are achieved, the faradic efficiency of the formate is about 80%, and the stability is up to 24 hours;
(2) The preparation method is simple, the obtained material is easy to apply, all reagents are commercial products, and the preparation method does not need further treatment and is favorable for popularization and application in industrial production;
drawings
FIG. 1 is XPS spectra of D-NR prepared in example 1 and D-NS electrocatalyst prepared in comparative example 1.
FIG. 2 is an XPS total spectrum of the D-NR prepared in example 1 and the D-NS electrocatalyst prepared in comparative example 1.
Fig. 3 is SEM and TEM images of NR prepared in example 1 and NS precatalyst prepared in comparative example 1.
FIG. 4 is SEM and TEM images of the D-NR prepared in example 1 and the D-NS electrocatalyst prepared in comparative example 1.
FIG. 5 is CO for the D-NR prepared in example 1 and the D-NS electrocatalyst prepared in comparative example 1 2 Comparative graph of electrocatalytic reduction performance.
FIG. 6 is XRD patterns of 30 minutes and 20 hours of testing of the D-NR prepared in example 1 and the D-NS electrocatalyst prepared in comparative example 1.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
Preparation of oxygen nano sheet-shaped bismuth-based material with high-concentration subsurface solvent
Step (1): dropwise adding a solution containing 2g of bismuth nitrate pentahydrate into a sodium diethyldithiocarbamate solution, wherein the molar ratio of the bismuth nitrate to the sodium diethyldithiocarbamate is 1. Washing and drying to obtain Bi (S) 2 CNEt 2 ) 3 Powder;
step (2): 0.65g of Bi (S) 2 CNEt 2 ) 3 Adding the nano rod-shaped bismuth sulfide into 10mL of deionized water, carrying out hydrothermal treatment at 140 ℃ for 10 hours, washing and drying to obtain nano rod-shaped bismuth sulfide (marked as NR);
and (3): 10mg of the prepared NR powder and 40. Mu.L of Nafion solution (5 wt%) were dispersed in 1mL of ethanol, and after sonication for 30 minutes, the solution was uniformly dropped on a hydrophobic carbon paper as a working electrode (drop area 1X 1 cm) 2 ). Using the above-mentioned electrode as working electrode, ag/AgCl (3M KCl) as referenceAnd (3) taking a platinum mesh electrode as a counter electrode, and carrying out electrolytic reduction for 30 minutes under the reduction potential of-1.0V (relative to the reversible hydrogen electrode) to obtain the nano flaky bismuth-based material (marked as D-NR).
The prepared bismuth-based nano material is in a nano sheet shape, the length and the width of the bismuth-based nano material are 1-10 mu m, and the thickness of the bismuth-based nano material is 20-50 nm.
Example 2
Preparation of oxygen nano sheet-shaped bismuth-based material with high-concentration subsurface solvent
Step (1): the solution containing 2g of bismuth chloride was added dropwise to the sodium diethyldithiocarbamate solution in a molar ratio of 1:1, the concentrations of the two being 0.2M, and stirred at room temperature for 1 hour. Washing and drying to obtain Bi (S) 2 CNEt 2 ) 3 Powder;
step (2): 0.4g of Bi (S) 2 CNEt 2 ) 3 Adding the bismuth sulfide into 10mL of deionized water, heating the mixture for 24 hours at 120 ℃, washing and drying the mixture to obtain nano rod-shaped bismuth sulfide (marked as NR 2);
and (3): 10mg of the prepared NR2 powder and 100. Mu.L of Nafion solution (5 wt%) were dispersed in 10mL of ethanol, and after sonication for 20 minutes, the resulting dispersion was uniformly applied dropwise onto a hydrophobic carbon paper as a working electrode (dropping area 1X 1 cm) 2 ). And (3) carrying out electrolytic reduction for 20 minutes under the reduction potential of-0.6V (relative to a reversible hydrogen electrode) by taking the electrode as a working electrode, ag/AgCl (3M KCl) as a reference electrode and a platinum mesh electrode as a counter electrode to obtain the nano flaky bismuth-based material.
Example 3
Preparation of oxygen nano sheet-shaped bismuth-based material with high-concentration subsurface solvent
Step (1): the solution containing 2g of bismuth nitrate was added dropwise to the sodium diethyldithiocarbamate solution at a molar ratio of bismuth nitrate to sodium diethyldithiocarbamate of 1:5, both concentrations being 0.05M, and stirred at room temperature for 2 hours. Washing and drying to obtain Bi (S) 2 CNEt 2 ) 3 A powder;
step (2): 1g of Bi (S) 2 CNEt 2 ) 3 Adding into 10mL deionized water, heating at 160 deg.C for 6 hr, washingWashing and drying to obtain nano rod-shaped bismuth sulfide (marked as NR 3);
and (3): 20mg of the prepared NR3 powder and 10. Mu.L of Nafion solution (5 wt%) were dispersed in 0.5mL of ethanol, and after ultrasonication for 60 minutes, the resulting dispersion was uniformly applied dropwise to a hydrophobic carbon paper as a working electrode (dropping area: 1X 1 cm) 2 ). And (3) carrying out electrolytic reduction for 60 minutes under the reduction potential of-1.0V (relative to a reversible hydrogen electrode) by taking the electrode as a working electrode, ag/AgCl (3M KCl) as a reference electrode and a platinum mesh electrode as a counter electrode to obtain the nano flaky bismuth-based material.
Comparative example 1
Preparation of oxygen nano sheet-shaped bismuth-based material with low-concentration subsurface solvent
Step (1): the solution containing 2g of bismuth nitrate pentahydrate was added dropwise to the sodium diethyldithiocarbamate solution and stirred at room temperature for 1 hour. Washing and drying to obtain Bi (S) 2 CNEt 2 ) 3 And (3) powder.
Step (2): 300mg of Bi (S) 2 CNEt 2 ) 3 Uniformly dispersing the bismuth sulfide into 30mL of ethylenediamine, heating the mixture at 180 ℃ for 2 hours in a solvent, washing and drying to obtain the nano flaky bismuth sulfide precatalyst (recorded as NS).
And (3): NS powder of step (2) 10mg and 40. Mu.L Nafion solution (5 wt%) were dispersed in 1mL of ethanol, sonicated for 30 minutes, and uniformly dropped on a hydrophobic carbon paper as a working electrode (drop area 1X 1 cm) 2 ). And (3) carrying out electrolytic reduction for 30 minutes under the reduction potential of-1.0V (relative to a reversible hydrogen electrode) by taking the electrode as a working electrode, ag/AgCl (3M KCl) as a reference electrode and a platinum mesh electrode as a counter electrode to obtain the nano flaky bismuth-based material (marked as D-NS).
The prepared bismuth-based nano material is in a nano sheet shape, the length and the width of the bismuth-based nano material are 1-10 mu m, and the thickness of the bismuth-based nano material is 20-50 nm.
Effect example 1
The prepared D-NR and D-NS electrocatalysts were respectively subjected to XPS test, and the chemical states of the elements in the catalysts were investigated by XPS (ESCALB 250 Xi) with the binding energy of the C1s peak set to 284.8eV as a reference, and FIG. 1 is O1s and Bi 4f of XPS spectra of the prepared D-NR and D-NS electrocatalysts. Peak of Bi-O bond of D-NR to peak of D-NSMore strongly, by comparing the O-Bi bonds (A) in FIG. 1a O-Bi ) To the general O bond (A) O ) Peak area ratio (R) of O ) To quantify the amount of O. Assuming that O is 100% bound, R of D-NR and D-NS O 15.2% and 4.6% respectively; by comparing the Bi-O bonds (A) in FIG. 1b Bi-O ) Bonded to total Bi (A) Bi ) Peak area ratio (R) of Bi ) To quantify the amount of O. Assuming that Bi is 100% bound, then R of D-NR and D-NS Bi 12.9% and 3.6%, respectively, indicating a higher oxygen concentration in the sub-surface solvent. And this is precisely D-NR electrocatalytic CO 2 The reduction performance is superior to the key factor of D-NS. FIG. 2 is an XPS summary spectrum of the prepared D-NR and D-NS electrocatalysts. No element S is detected, and the nano-rod-shaped bismuth sulfide precatalyst is proved to be converted into a bismuth-based material in the electro-reduction process.
Effect example 2
SEM and TEM characterization of the prepared pre-catalysts NR and NS and the electrocatalysts D-NR and D-NS were performed. The structure of the catalyst was characterized by SEM (S-3400N) and TEM (TECNAI F-30, 300 kV). Fig. 3a, 3b and 3c are SEM, TEM and HRTEM images, respectively, of the prepared NR precatalyst. The length of NR is 1-7 μm, and the width is 50-400 nm. The lattice spacing of NR is 0.81nm, and Bi 2 S 3 Corresponds to (110) plane. Selected area electron diffraction accounts for its single crystal nature. Fig. 3d, 3e and 3f are SEM, TEM and HRTEM images, respectively, of the prepared NS precatalyst. The NS diameter is in the order of microns. Lattice spacing of NS is 0.32nm, and Bi 2 S 3 Corresponds to (130) plane. Selected area electron diffraction accounts for its single crystal nature. Fig. 4a and 4b are SEM and TEM images of the prepared D-NR electrocatalyst, respectively. SEM shows that the bismuth sulfide nanometer rod-shaped pre-catalyst is converted into nanometer sheet structure with the diameter of 1-10 nm, and selective electron diffraction shows the single crystal characteristic. Fig. 4c and 4D are SEM and TEM images of the prepared D-NS electrocatalyst, respectively. SEM shows that it retains a nano-platelet structure and selective electron diffraction indicates its single crystal nature.
Effect example 3
In an H-type electrolytic cell separated by a Nafion115 exchange membrane, a standard three-electrode system is adopted, D-NR and D-NS are respectively used as working electrodes, and Ag-AgCl (3M KCl) as reference electrode, platinum mesh electrode as counter electrode, and 0.5M KHCO as cathode channel 3 Introducing CO into the electrolyte 2 To saturation, and then CO is carried out by controlling the reduction potential to-0.8 to-1.2V (relative to a reversible hydrogen electrode) 2 And (5) testing the reduction performance.
FIG. 5 CO of the prepared D-NR electrocatalyst 2 And comparing the electrocatalytic reduction performance. In CO 2 Saturated 0.5M KHCO 3 In solution, D-NR undergoes CO in the range of-0.8 to-1.2V (relative to a reversible hydrogen electrode) 2 Electrocatalytic reduction test. LSV polarization curves show that D-NR does have CO 2 Electrocatalytic reduction activity (fig. 5 a). The reduction product is C 1 Products (formate and CO) and H 2 . In the potential range of-0.8 to-1.2V (relative to reversible hydrogen electrode), C 1 The faradaic efficiency of the product was higher than 70%, reaching an optimum of about 82% at-1.0V (relative to the reversible hydrogen electrode) (fig. 5 b). The current density reaches-11 mA cm at-1.2V (relative to a reversible hydrogen electrode) -2 Above, this illustrates the CO of D-NR 2 The reduction activity and selectivity were excellent (fig. 5 c). In addition to good activity and selectivity, D-NR also has long-term durability. CO at-1.0V (vs. reversible hydrogen electrode) for up to 24 hours 2 And (4) electrocatalytic reduction. D-NR shows stable performance in this process. Within 24 hours of the test (measured every 1 hour), there was no significant decay in current density, and C 1 The corresponding faradaic efficiency of the product was always greater than 77% (fig. 5 d). As a result, it was confirmed that D-NR is an excellent CO resistance 2 Reduced, persistent electrocatalysts.
FIG. 5 CO of the prepared D-NS electrocatalyst 2 And comparing the electrocatalytic reduction performance. LSV polarization curve surface D-NS does have CO 2 Electrocatalytic reduction activity (fig. 5 a). The reduction product is C 1 Products (formate and CO) and H 2 . In the potential range of-0.8 to-1.2V (relative to reversible hydrogen electrode), C 1 The faradaic efficiency of the product was below 40% (FIG. 5 b) and the current density was below-6 mA cm -2 (FIG. 5 c), which illustrates the CO of D-NS 2 The reduction activity and selectivity are far from those of D-NR. CO at-1.0V (vs. reversible hydrogen electrode) for up to 16 hours 2 And (4) carrying out electrocatalytic reduction. The current density of the D-NS electrocatalyst showed a significant drop after 15 hours, and C 1 The corresponding FEs of the products were all below 40% (fig. 5D), which demonstrates that the D-NS electrocatalyst is unstable. D-NR electrocatalysts with higher concentrations of oxygen in the sub-surface solvent exhibit better activity and stability compared to D-NS.
Effect example 4
The prepared D-NR and D-NS electrocatalysts were subjected to XRD testing to determine the crystal structure using X-ray diffraction (D/MAX 2550 VB/PC), and FIG. 6 is an XRD pattern of the prepared D-NR and D-NS electrocatalysts tested for 30 minutes and 20 hours. It was demonstrated that bismuth oxide formed during electrocatalysis remained on the material.

Claims (15)

1. The preparation method of the bismuth-based nano material is characterized by comprising the following steps: preparing nano-rod-shaped bismuth sulfide into a nano-sheet bismuth-based material by an electrochemical reduction method; the nano-rod-shaped bismuth sulfide is Bi (S) 2 CNEt 2 ) 3 Prepared by a hydrothermal method;
the electrochemical reduction method is a method for electrochemically reducing bismuth sulfide into bismuth/bismuth oxide;
the electrochemical reduction method comprises the following steps: dispersing nano-rod-shaped bismuth sulfide and 5wt% of perfluorosulfonic acid-polytetrafluoroethylene copolymer solution in ethanol, performing ultrasonic treatment to prepare a working electrode, and performing in-situ electrochemical reduction by using 3M KCl Ag/AgCl as a reference electrode and a platinum electrode as a counter electrode.
2. The method for preparing bismuth-based nanomaterial of claim 1, wherein the nano-rod-shaped bismuth sulfide has a length ranging from 1 μm to 7 μm and a width ranging from 50nm to 400nm.
3. The method of preparing the bismuth-based nanomaterial of claim 1, wherein the hydrothermal process has a temperature ranging from 120 to 160 ℃ and a time ranging from 6 to 24 hours;
and/or, the Bi (S) 2 CNEt 2 ) 3 And in the hydrothermal processThe dosage of the deionized water is 4 to 10g/100mL;
and/or, the Bi (S) 2 CNEt 2 ) 3 The bismuth-source precursor solution and the sulfur-source precursor solution are mixed to prepare the bismuth-source composite material.
4. The method for preparing bismuth-based nanomaterial of claim 3, wherein the hydrothermal process is carried out at a temperature of 140 ℃ for a time of 10 hours;
and/or, the Bi (S) 2 CNEt 2 ) 3 The amount of deionized water used in the hydrothermal process was 6.5g/100mL.
5. The method for preparing the bismuth-based nanomaterial of claim 3, wherein the bismuth-source precursor is selected from bismuth nitrate and/or bismuth chloride; the sulfur source precursor is sodium diethyldithiocarbamate;
and/or the molar ratio of the bismuth source precursor to the sulfur source precursor is 1:1 to 1:5;
and/or the concentration of the bismuth source precursor is 0.1mol/L; the concentration of the sulfur source precursor is 0.1mol/L;
and/or the solvent in the solution of the bismuth source precursor and the solution of the sulfur source precursor is water or methanol;
and/or, the mixing means stirring at room temperature.
6. The method for preparing the bismuth-based nanomaterial of claim 5, wherein the bismuth source precursor is bismuth nitrate pentahydrate;
and/or the molar ratio of the bismuth source precursor to the sulfur source precursor is 1:3;
and/or, room temperature means at 25 ℃.
7. The method for preparing bismuth-based nanomaterial of claim 3, wherein the Bi (S) 2 CNEt 2 ) 3 The preparation method comprises the following steps: 33mL of 0.1mol/L bismuth source precursor solution was added dropwise to 100mL of 0.1mol/L diethyl disulfideIn sodium carbamate solution.
8. The method for preparing the bismuth-based nanomaterial of claim 1, wherein the platinum electrode is a platinum mesh.
9. The method for preparing bismuth-based nanomaterial of claim 1, wherein the nano-rod-shaped bismuth sulfide and 5wt% perfluorosulfonic acid-polytetrafluoroethylene copolymer solution are used in an amount of 0.1 to 2mg/μ L;
the dosage of the nano rod-shaped bismuth sulfide relative to ethanol is 1-50 mg/mL;
the ultrasonic frequency is 10-50 KHz, and the ultrasonic time is 20-60 minutes.
10. The method for preparing bismuth-based nanomaterial of claim 9, wherein the nano-rod-shaped bismuth sulfide and 5wt% perfluorosulfonic acid-polytetrafluoroethylene copolymer solution are used in an amount of 0.25mg/μ L;
and/or the dosage of the nano rod-shaped bismuth sulfide relative to ethanol is 10mg/mL;
and/or the ultrasonic frequency is 40KHz, and the ultrasonic time is 30 minutes.
11. The method for preparing the bismuth-based nanomaterial of claim 1, wherein the working electrode is prepared by uniformly dripping the ethanol dispersion on hydrophobic carbon paper;
the electrochemical reduction has a reduction potential of-0.6 to-1.0V relative to the reversible hydrogen electrode;
the time for the electrochemical reduction is 20 to 60 minutes.
12. The method for preparing the bismuth-based nanomaterial of claim 11, wherein the area of the droplet coating is 1 x 1cm 2 ；
And/or the reduction potential is-1.0V;
and/or the time of the electrochemical reduction is 30 minutes.
13. A bismuth-based nanomaterial prepared by the method of preparing a bismuth-based nanomaterial according to any one of claims 1 to 12.
14. The bismuth-based nanomaterial of claim 13, wherein the bismuth-based nanomaterial is a nanosheet shape, having a length of 1 μm to 10 μm, a width of 1 μm to 10 μm, and a thickness of 20nm to 50nm.
15. The use of the bismuth-based nanomaterial of claim 13 or 14 in electrocatalysis of CO 2 The application as a catalyst in reduction.
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